Recyclable metathesis catalysts

ABSTRACT

Highly active, recoverable and recyclable transition metal-based metathesis catalysts and their organometallic complexes including dendrimeric complexes are disclosed, including a Ru complex bearing a 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene and styrenyl ether ligand. The heterocyclic ligand significantly enhances the catalytic activity, and the styrenyl ether allows for the easy recovery of the Ru complex. Derivatized catalysts capable of being immobilized on substrate surfaces are also disclosed. The present catalysts can be used to catalyze ring-closing metathesis (RCM), ring-opening (ROM) and cross metatheses (CM) reactions, and promote the efficient formation of various trisubstituted olefins at ambient temperature in high yield.

RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/224,305 filed on Aug. 10, 2000 and U.S. ProvisionalApplication No. 60/264,361 filed on Jan. 26, 2001.

GOVERNMENT SUPPORT

[0002] This invention was supported by a grant from the National ScienceFoundation. The government has certain rights in this invention.

BACKGROUND OF THE INVENTION

[0003] Metal-catalyzed olefin metathesis reactions serve as aspringboard for the development of a range of regioselective andstereoselective processes. These processes are important steps in thechemical synthesis of complex organic compounds and polymers. Inparticular, these reactions often are crucial steps in medicinalchemistry for small molecule synthesis. Organo-metallic catalysts,particularly transition metal complexes based on osmium, ruthenium ortungsten, are used in many such organic transformation reactions.

[0004] The synthesis and catalytic activity of ruthenium-based complexeswhich can efficiently catalyze ring-opening metathesis (ROM) andring-closing metathesis (RCM) of dienes that contain terminal olefinshas been reported for example, by Kingsbury, J. S.; Harrity, J. P. A.;Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799;Harrity, J. P. A.; Visser, M. S.; Gleason, J. D.; Hoveyda, A. H. J. Am.Chem. Soc. 1997,119, 1488-1489; and Harrity, J. P. A.; La, D. S.;Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998,120, 2343-2351. Because of the risk of metal contamination of theresulting product, and due to the cost of organometallic catalysts,recovery and reuse of such catalysts is important. Kingsbury, et al.showed that an organometallic rutheniun-based catalyst could berecovered from the reaction mixture by silica gel chromatography in highyield and reused in subsequent C-C bond forming reactions. Kingsbury etal., supra. However, there are several shortcomings in the prior antrecyclable metathesis catalyst, including that it is useful mostly forsubstrates that contain terminal alkenes. In certain cases, due toco-elution, isolation of the catalyst from the substrate is problematic.

SUMMARY OF THE INVENTION

[0005] The present invention comprises highly active and recyclabletransition metal-based metathesis catalysts, methods of making suchcatalysts and their use in metathesis reactions. The catalysts of thepresent invention are organometallic complexes of a transition metalcomprising an organic ligand that permits recovery of the catalyst metalfrom the reaction mixture. The organometallic complexes of the inventioncan be in monomeric, polymeric and dendritic forms that are capable ofpromoting various forms of metathesis reactions in a highly efficientmanner, and can be efficiently recovered from the reaction mixtures andreused; they are therefore, recyclable. Unlike prior recoverabletransition metal-based complexes, the catalysts of the present inventioneffect the efficient formation of trisubstituted alkenes andtetrasubstituted olefins through catalytic metathesis processes. Thepolymeric and dendritic catalysts of the invention offer the addedadvantage that they are more readily isolable. The present catalysts areextremely active (can be used to prepare tri- and tetra-substitutedolefins), can be readily recovered and reused and leave little or notrace of toxic metal contamination within the product.

[0006] In one aspect, the invention comprises a composition comprising amonomeric catalyst having the following Formula I:

[0007] wherein:

[0008] M is a transition metal;

[0009] X comprises oxygen (O), sulfur (S), nitrogen (N) or phosphorus(P);

[0010] R comprises an alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy,alkynyloxy, aryloxy, alkoxy carbonyl, alkylamino, alkylthio,alkylsulfonyl, alkylsulfinyl; each optionally substituted with an alkyl,halogen, alkoxy, aryl or heteroaryl moiety;

[0011] R₁ and R₂ each comprise, or together comprise, an electronwithdrawing anionic ligand;

[0012] a, b, c, and d each comprises H, a halogen atom or an alkyl,alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy,alkoxycarbonyl, alkylamino, alkylthio, alkylsulfunyl; alkylsulfinyl;each optionally substituted with an alkyl, halogen, aryl or heteroarylmoiety; and

[0013] Y comprises an electron-donating heterocyclic carbene ligand.

[0014] In a preferred embodiment, M is ruthenium, X is O, R is a loweralkyl group (e.g., C₁-C₁₂), R₁ and R₂ are halogen atoms (which may beidentical or different but preferably are identical), a, b, c and d eachcomprises hydrogen or a lower alkyl group (e.g., C₁-C₁₂), and Ycomprises a 4,5-dihydroimidazol-2-ylidene carbene ligand ring structureor a phosphine moiety. In a more preferred embodiment, M is ruthenium, Xis O, R is isopropyl, R₁ and R₂ are chlorine atoms (Cl), a, b, c and deach comprises hydrogen, and Y comprises a heterocyclic ring structurehaving the following Formula II:

[0015] wherein R₃ and R₄ comprise he same or different aromatic ringmoieties. In currently preferred embodiment, R₃ and R₄ comprise2,4,6-trimethylphenyl (mesityl) moieties.

[0016] In another aspect, the invention comprises dendritic catalyststructure having the following Formula III:

[0017] wherein R₅, R₆, R₇ and R₈ each comprises the following FormulaIV:

[0018] wherein:

[0019] M comprises a transition metal,

[0020] X comprises O, S, N or P;

[0021] R comprises an alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy,alkynyloxy, aryloxy, alkoxy carbonyl, alkylamino, alkylthio,alkylsulfnyl, alkylsulfinyl; each optionally submitted with an alkyl,halogen, aryl or heteroaryl moiety;

[0022] R₁ and R₂ each comprises, or together comprise, an electronwithdrawing group; and Z comprises Y or a phosphine group.

[0023] In a preferred embodiment, M is Ru, X is O, R is a lower alkylgroup (e.g., C₁-C₁₂), R₁ and R₂ are halogen atoms (which may beidentical or different but preferably are identical), and Z comprises aphosphine moiety having the formula P(Cy)₃, wherein Cy comprises analiphatic ring structure, preferably cyclohexyl or cyclopentyl. In acurrently preferred embodiment, M is Ru, X is O, R is isopropyl, R₁ andR₂ each is a chlorine atom (Cl), and Z is P(cyclohexyl)₃.

[0024] In another preferred embodiment, M is Ru, X is O, R is a loweralkyl group (e.g., C₁-C₁₂), R₁ and R₂ are halogen atoms and Z comprisesa ring structure having Formula II wherein R₃ and R₄ comprise the sameor different aromatic ring moieties. In a currently preferredembodiment, M is Ru, X is O, R is isopropyl, R₁ and R₂ are chlorineatoms (Cl) and Z comprises a ring structure having Formula II wherein R₃and R₄ both comprise a 2,4,6-trimethyl phenyl (mesityl) moiety.

[0025] The present invention provides stable, readily recoverabletransition metal-based metathesis catalysts with high catalyticactivity. The catalysts may be used free in the reaction mixture or maybe immobilized on a solid phase. In another aspect of the invention, themonomeric catalysts of Formula I are immobilized on a solid phase. In apreferred embodiment, the catalysts of the invention are immobilized onsolid phases such as, for example, metals, glass, polymers, ceramics,organic polymer beads, inorganic sol-gels or other inert substances,without impairing their ability to catalyze various forms of metathesisreactions in a highly efficient manner. In a currently preferredembodiment, the solid phase is an inorganic sol gel such as, forexample, a glass monolithic gel. In addition, the invention comprisesthe design and synthesis of various chiral versions of the presentmonomeric and dendritic complexes and their application to asymmetriccatalytic metathesis.

[0026] Immobilization of catalysts of the invention to an inorganicmonolithic gel provides the following advantages over immobilization ofsuch catalysts on conventional solid phases such as organic polymerbeads: (1) overcomes limitations of organic polymer beads such asvariable swelling and shrinking in different media, often resulting inreduction of catalytic activity (2) precludes the addition ofsignificant volumes of solvents needed for recovery of beads bound tothe catalyst, a necessity that seriously limits the utility ofrecoverable surface immobilized catalysts, thereby detracting from thepracticality of such an approach and rendering it more costly andenvironmentally less friendly. (3) The high porosity characteristic ofinorganic gels translates to a substantially large interfacial surfacearea (typically 300-1000 m²/g), rendering such materials ideal forimmobilization of catalysts of the invention. (4) Gelation occurs aftera sol is cast into a mold; it is, therefore, possible to tailor the gelsamples to a desired shape or even function.

[0027] In another preferred embodiment, the surface immobilizedcatalysts of the present invention is an integral part of the reactionapparatus itself, thus obviating the need for a filtration step torecover the catalyst after completion of metathesis processes. Processesof the present invention are, therefore, rendered operationally simplefrom the standpoint of both execution and work-up.

[0028] The recyclable catalysts of the present invention aresubstantially more active than prior art recyclable metathesiscatalysts. The transition metal-based monomers and dendrimers of thepresent invention are easily characterizable and serve as homogeneousmetathesis catalysts that are highly active and allow for significantlymore facile catalyst recovery compared to prior art catalysts.

BRIEF DESCRIPTION OF THE FIGURES

[0029]FIG. 1 shows two prior art ruthenium catalysts: (1) is arecoverable complex of ruthenium with an isopropoxystyrene and aphosphine moiety, and (2) is a benzylidene catalyst.

[0030]FIG. 2 shows an ORTEP diagram of Cl₂Ru(═CH-o-OiPrC₆H₄)(4,5-dihydrolMES) (Formula 5). Thermal ellipsoids are drawn at 30%probability level, and selected bond distances and angles are shown inTable 1.

[0031]FIG. 3 shows the transition metal catalysts (1, 2) andorganometallic compound 2a comprising an active metal complex.

[0032]FIG. 4 shows surface immobilized catalysts of the inventioncoupled to a solid phase (represented by a spherical solid substrated)via different types of linkers.

DETAILED DESCRIPTION OF THE INVENTION

[0033] The present invention comprises a novel class of recoverable andrecyclable organometallic metathesis catalysts. The term “recoverable”as used herein means that the catalyst can be recovered or retrievedfrom the reaction mixture once the reaction is complete. The term“recyclable” means that the recovered catalyst can be reused insubsequent metathesis reactions after recovery from the previousreaction(s).

[0034] The catalysts of the present invention comprise novel monomericcatalysts having the structure of Formula I, and dendritic catalystshaving the structure of Formula III. The present monomeric and dendriticcatalysts are recoverable and recyclable, and can efficiently catalyze avariety of olefin metathesis reactions, including ring-openingmetathesis (ROM), ring-closing metathesis (RCM), cross-metathesis (CM),ring-opening polymerization metathesis (ROMP), and acyclic dienemetathesis (ADMET). The catalysts of the present invention can be usedin most metathesis reactions under appropriate conditions. Those skilledin the art would be able to empirically determine the amount of catalystand optimal conditions of the reaction. For example, the monomeric anddendritic catalysts of the present invention can be used in mostreactions at levels of from about 1.0 mol % to about 5.0 mol %.

[0035] The present catalysts can be recovered from the reaction mixtureby any technique suitable for recovering or separating organometalliccomplexes, including chromatography or filtration. For example, themonomeric or dendritic catalysts may be separated form the reactionmixture by silica gel chromatography. If the catalyst is attached to asolid phase, as described below, then the catalyst can be recovered byseparating the solid phase from the reaction mixture by simplefiltration.

[0036] Monomeric complexes. In one aspect, the present inventionprovides monomeric catalysts having the structure shown as Formula I.Monomeric catalysts having Formula I can be prepared according theprocedures shown in Equation 1 below, in Examples 1-10, or via othersynthetic routes that would be readily ascertainable by those skilled inthe art.

[0037] The structure shown as Formula 5 in Equation 1 below comprises acurrently preferred embodiment of the present invention.

Equation 1

[0038] Synthesis of Formula 5. The catalyst of Formula 5 was synthesizedand characterized, and its reactivity and recyclability were determined.It was determined that the saturated imidazolin-2-ylidene andunsaturated imidazol-2-ylidene carbene ligands accelerated themetathetic activity of Ru-based complexes. As depicted in Equation 1,treatment of compound 3 with 2.5 equivalents CuCl and 0.97 equivalentsof compound 4 in CH₂Cl₂ at 40° C. delivers the Formula 5 catalyst within1 hour; the Formula 5 catalyst was isolated as an air stable green solidin quantitative (>98%) yield after silica gel chromatography(mp=178-181° C. dec).

[0039] Single-crystal X-ray structure analysis of a Formula 5 catalystis shown in FIG. 2;(IMES=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene). The crystalstructure analysis confirms the structural assignment shown in Formula5. Selected bond lengths and angles for Formula 5 are provided inTable 1. The overall geometry around the transition metal center andmost of the bond angles and bond lengths in Formula 5 are analogous totheir related values in the complex of Formula 6 (shown in Scheme 1).

[0040] Comparison of the ¹H NMR spectra of prior art compound 1 (shownin FIG. 1) and the Formula 5 catalyst show some of the differentialstructural attributes of these complexes. As illustrated in Scheme 1,there are two distinct chemical shift changes in the 400 MHz ¹H NMRspectra of Formula 5 catalyst and compound 1. One variation is observedat the iso-Pr methine proton and another at the carbene CH (H_(α)). Inboth instances, the protons for the imidazolin-2-ylidene system inFormula 5 are more shielded. These differences may be attributed tohigher electron density at the transition metal center of Formula 5,caused by the stronger electron donation by the heterocyclic ligand(compared to PCy₃ (Cy is an aliphatic cycloalkyl moiety, preferablycyclohexyl). The weaker electron donation by the oxygen ligand to the Rucenter in Formula 5 may be manifested by the more upfield appearance ofthe isopropyl methine proton (5.28 vs 4.90 ppm). TABLE 1 Selected BondLengths and Angles for Cl₂Ru (═CH—o—OiPrC₆H₄)(4,5-dihydrolMES) (Formula5) Bond lengths (Å) Ru(1)-C(1) 1.828(5) Ru(1)-Cl(1) 2.328(12) Ru(1)-C(2)1.981(5) Ru(1)-Cl(2) 2.340(12) Ru(1)-O(1) 2.261(3) C(2)-N(1) 1.351(6)C(2)-N(2) 1.350(6) Bond angles (deg) C(1)-Ru(1)-O(1) 79.3(17)O(1)-Ru(1)-Cl(1) 86.9(9) C(1)-Ru(1)-C(2) 101.5(14) O(1)-Ru(1)-C1(2)85.3(9) C(2)-Ru(1)-O(1) 176.2(14) C(2)-Ru(1)-Cl(1) 96.6(12)C(1)-Ru(1)-Cl(1) 100.2(15) C(2)-Ru(1)-C(2) 90.9(12) C(1)-Ru(1)-C1(2)100.1(15) Cl(1)-Ru(1)-Cl(2) 156.5(5) N(1)-C(2)-N(2) 106.9(4)

[0041] Comparison of the ¹H NMR spectra of prior art compound 1 (shownin FIG. 1) and Formula 5 shows some of the structural attributes ofthese complexes. As illustrated in Scheme 1, there are two distinctchemical shift changes in the 400 MHz ¹H NMR spectra of Formula 5 andcompound 1.

[0042] One variation is observed at the iso-Pr methine proton andanother at the carbene CH (H_(α)). In both instances, the protons forthe imidazolin-2-ylidene system in Formula 5 are more shielded. Thesedifferences may be attributed to higher electron density at thetransition metal center of Formula 5, caused by the stronger electrondonation by the heterocyclic ligand (compared to PCy₃ (Cy is analiphatic cycloalkyl moiety, preferably cyclohexyl). The weaker electrondonation by the oxygen ligand to the Ru center in Formula 5 may bemanifested by the more upfield appearance of the isopropyl methineproton (5.28 vs 4.90 ppm).

[0043] Catalytic Activity and Recovery of Formula 5 catalyst. The datain Table 2 below illustrate that the Formula 5 catalyst is an effectivecatalyst for RCM of dienes. In this reaction, hetero- and carbocycliccompounds bearing trisubstituted alkenes were obtained from thecorresponding precursor dienes in the presence of 5 mol % catalyst atambient temperature within 10 mm to 2 h. As shown in entries 1 and 2 ofTable 2, both 1,1-disubstituted (7) and trisubstituted olefins (9) maybe utilized in the synthesis of trisubstituted cyclic alkenes. Thecatalytic RCM in entries 3-4 indicate that trisubstituted allylicalcohols (12) and acetates (14) can be accessed in the presence of 5 mol% 5 within 2 h. The Ru catalyst of Formula 5 is recovered with highefficiency (95% and >98% yield, respectively). The prior art catalyst 1is significantly less efficient in promoting the above transformations.As an example, treatment of structure 11 with 5 mol % 1 (22 EC, CH₂Cl₂)leads to only 15% conversion after 2 h (as judged by 400 MHz ¹NMR).

[0044] Two important points in connection to the above data areimportant:

[0045] (1) In all instances, the catalyst is recovered, along with thedesired cyclic product in high yield after simple silica gelchromatography. Moreover, addition of 2 equivalents of styrene ether 4(relative to the catalyst) to a solution of a transformation promoted bythe non-recyclable 3 at the end of the reaction time, leads to theisolation of the recyclable catalyst 5. As an example: Treatment ofdiene carbinol 11 is treated with 5 mol % 3 (CH₂Cl₂, 22EC, 1 h),followed by the addition of 10 mol % 4 and addition stirring for 1 h,leads to the formation of 12 and 5 in 98% and 82% yields, respectively(after silica gel chromatography).

[0046] (2) Catalyst loading lower than 5 mol % is sufficient. Asexemplified by the reaction in entry 2, catalytic RCM can readilyproceed to completion with only 1 mol % Formula 5 catalyst. As anotherexample, catalytic RCM of 7 occurs within 10 mm at 22° C. in thepresence of 1 mol % of 5 to afford 8 in 73% isolated yield (>98% conv);recovered 5 is obtained in 92% yield after chromatography.

[0047] As the reaction in entry 5 of Table 2 indicates,tetra-substituted olefins can also be obtained through catalytic RCMpromoted by the catalyst of Formula 5. TABLE 2 Ring-Closing Metathesisof Acyclic Dienes by Ru Complex 5^(a) product catalyst entry substrateproduct time conv (%) yield (%)^(b) recovery (%)^(b) 1

10 min >98 82  98 2

20 min >98 87  98 3

2 h >98 75  95 4

1.5 h >98 82 >98 5

44 h  42 38  81 6

30 min  70 65  60

[0048] In this instance, the Ru catalyst is recovered in >80% yield.When toluene is used as the solvent in the catalytic RCM of compound 17,tetrasubstituted alkene 18 is formed in 65% isolated yield within 30minutes (70% conversion).

[0049] The catalysts used the above-described transformations may beretrieved from the reaction mixture, e.g., using silica gelchromatography, and then may be used in subsequent metathesis reactionswith equal efficiency and without recrystallization. For example, thecatalyst recovered from the reaction in entry 1 of Table 2 was reused inthe same reaction to afford the desired product 8 in 71% isolated yield(10 minutes, 22° C.). The Formula 5 catalyst was again recovered in 98%yield after chromatography.

[0050] As shown by the representative transformations in Scheme 2,Formula 5 also is an efficient catalyst in ROM/RCM and ROM/CM processes.Both transformations were completed within 1 hour, with >98% conversion.

[0051] Scheme 3 shows the release/return mechanism by which the presentmonomeric catalysts function as metathesis catalysts. As shown therein,a diene substrate probably first reacts with the initial Ru complex toremove the transition metal from the styrene ligand and “release” thestyrene ether 4. Upon consumption of the diene, the active Ru-carbenereacts with the previously occupied styrenyl ether to cause reformationor “return” of the initial complex.

[0052] Dendritic complexes. In another aspect, the present inventionprovides dendritic catalysts having the structure shown as Formula III.Dendritic catalysts having Formula III can be prepared according theprocedures described below, in Examples 11-16, or via other syntheticroutes that would be readily ascertainable to these skilled in the art.

[0053] The structures shown as Formulae 30 and 31 below comprisecurrently preferred embodiments of the present invention.

[0054] Dendritic complexes, due to their different polarity compared tothe monomeric species, generally can be more easily separated fromreaction products. With dendrimers, it is possible to gauge morerigorously the efficiency with which the active metal-carbene leaves theligation site and returns to the catalyst macromolecule. In additionboth the release of the metal center from the styrenyl ligand(initiation) and the return of the active metal to the initial site(recovery), which is shown in Scheme 3 above, are more efficient withthe more accessible and exposed terminal sites within the dendrimerstructure.

[0055] Synthesis of Ru-Containing Dendrimers. In a currently preferredembodiment, the dendrimers are tetraalkylsilyl systems. Scheme 4 belowshows a synthetic scheme for synthesizing a preferred Ru-containingdendrimer (Formula 30).

[0056] a. anhydrous HCl, i-PrOH, >87%, b, 2 equiv NaH, 2 equiv i-PrI,DMF, THF, 89%. c. 1.1 equiv Br₂, HOAc, CH₂Cl₂, 98%. d. 1.1 equivBu₃SnCHCH₂, 3 mol % Pd(PPh₃)₄, 2 mol % BHT, tol, 110° C., 4h, >98%. g.4.3 equiv Hme₂SiCl, 5 mol % H₂PtCl₆ in THF, 3h. h. 4.2 eqivCH₂CHCH₂MgBr, Et₂O, 22° C., 3h, >90% overall for two steps. i. 5.1 equiv9-BBN, THF, 22° C., 17 H; NaOH, H₂O₂, EtOH, THF, 22° C., 6 h, 96%. J.4.9 equiv EDC.HCl, 4.5 equiv 26, 0.6 equiv DMAP, 22° C., 3 h, 63%. k.4.3 equiv 2, 4.6 equiv CuCl, CH₂Cl₂, 22° C., 3 h, 83%.

[0057] The key features of the synthesis shown in Scheme 4 include theattachment of the requisite vinyl group through a pallidium(Pd)-catalyzed Stille coupling (26) and preparation of the dendrimerbackbone by a platinum (Pt)-catalyzedhydrosilation/alkylation/hydroboration sequence (27 28 29). Coupling of29 with four equiv 26, followed by incorporation of the RU centerthrough treatment with 2 in the presence of CuCl affords the desired 30as an air stable brown solid (mp=92-98° C. dec.).

[0058] Another preferred Ru-containing dendrimer, Formula 31, can beprepared as an air stable dark green solid by the same sequence ofreactions as shown in Scheme 4, except that the last step involvestreatment of the vacant dendritic structure with 4.3 equiv 3 and 4.6equiv CuCl in CH₂Cl₂ for 10 mm (55% yield; mp=114-117° C. dec).

[0059] Catalytic RCM, ROM and CM Promoted by Dendritic Catalysts ofFormulae 30 and 31. Table 3 below illustrates the use of the presentdendritic catalysts in a RCM reaction. As shown in table 3, treatment ofdiene 32 with 1.25 mol % of 30 (5 mol % Ru) leads to efficient andcatalytic RCM. The desired product (33) is first isolated in 99% yieldby silica gel chromatography through elution with CH₂Cl₂ subsequent washof the silica with Et2O leads to the isolation of the dendritic catalyst(>98% mass balance). Recovered 30 was analyzed by 400 MHz ¹H NMRspectroscopy; the resulting spectrum indicated that 13% of the styrenylligands were vacant (approximately 13% Ru loss).

TABLE 3 Utility of Dendritic Catalyst Formula 30 in Catalyzing RCMproduct yield^(a) Ru content^(b) Cycle (%) (%) 1 99 87 2 91 76 3 96 72 489 64 5 92 48 6 87 41

[0060] As illustrated in Table 3, repeated use of Formula 30 as acatalyst results in complete conversion of 32 to 33 and isolation of thedesired product in >86% isolated yield. These data thus illustrate thatdendrimer 30 is effective in promoting the catalytic RCM of terminaldienes in a highly efficient manner, and can be easily recovered bysimple silica gel filtration and reused repeatedly in subsequentreactions. In addition, after repeated use, the partially depleteddendrimer complex can be easily re-metaflated upon treatment with theappropriate equivalents of 3 and CuCl in CH₂Cl₂. The dendritic complexremains active even after nearly 50% of the Ru content has been depleted(see cycle 6 in Table 3). This level of reactivity may be attributed, atleast partially, to the fact that 30 (similar to monomeric catalysts 1and 5) releases a highly active mono-phosphine Ru complex into thesolution. In the absence of a second equivalent of PCy₃ that canre-coordinate to Ru and retard its catalytic activity (which is the casewhen 2 or 3 are used as catalysts), and since styrene ethers probably donot kinetically re-associate with Ru as efficiently as PCy₃, even asmall amount of Ru release can lead to substantial amounts of metathesisactivity.

[0061] Metal crossover experiments were carried out as depicted inScheme 5. Treatment of compound 4 with dendritic Ru complex of Formula30 results in little or no metal crossover (<2% 1 formed by 400 MHz ¹HNMR analysis). The amount of Ru bound to the dendritic vs monomericligands is readily determined by the chemical shift difference in the ¹HNMR spectra of the corresponding carbene CH (Ru═C(H)). When dienesubstrate 32 is treated with 1.25 mol % fully loaded 30 and 4 mol % 4,RCM product 33 is obtained within 15 mm. However, recovered 30 bears 42%less Ru, compared to 13% metal reduction when the reaction is carriedout in 4 (see Table 3, cycle 1). In addition, 30% of uncomplexed 4 isisolated after the reaction; the remainder of the monomeric styrenylalkoxide is recovered as monomeric Ru complex 1. These observationsindicate that the Ru metal, after reacting with the diene substrate andleaving the dendrimer, can be trapped again by a styrenyl alkoxide.Thus, in the absence of compound 4, the catalytically active Rumonophosphine would likely return to a styrene unit within the dendriticstructure.

[0062] Dendrimer 31 exhibits catalytic activity higher than thatobserved for 30. Unlike 1 or 30, but similar to 5, dendritic 31efficiently promotes the formation of trisubstituted allylic alcohol 12(Scheme 4); in addition to the desired product (78%), the dendrimer isrecovered after silica gel chromatography quantitatively with 8% loss inRu loading (judged by analysis of 400 MHz ¹H NMR). Moreover, as shown inEquation (5), similar to 5, dendrimer 31 effectively catalyzes tandemROM/RCM of 19 and the formation of 20 (94%). However, in contrast to thecorresponding monomer 5, dendrimer 31 can be easily separated from 20and recovered in 90/s yield (8% Ru loss). The transformation in Scheme 6indicates that 31 effectively promotes catalytic ROM/CM reactions aswell, and as before, it can be recovered readily and in good yield (>98%trans olefins in 22 and 34, as judged by 400 MHz ¹H NMR analysis). Thus,dendritic catalyst 31 retains the high activity of monomeric 5 andprovides the valuable practical advantage of being readily separablefrom metathesis products.

[0063] Similar to monomeric 5, lower loadings of 31 are sufficient forefficient catalytic metathesis. As an example, when triene 7 is treatedwith 0.25 mol % 31 (CH₂Cl₂, 22° C.) for 10 mm, RCM adduct 8 is formedwith >98% cony. In addition to dihydrofuran 8, isolated in 84% yield,recovered 31 is obtained in 88% yield after silica gel chromatography(22% Ru loss).

[0064] Immobilization of the Catalysts on a Solid Phase. The presentcatalysts can be attached to or immobilized on a solid support for usein metathesis reactions. Solid phases which can be used include, forexample, metals (including magnetic media), glass, polymers, ceramics orother inert substances that will not affect the reaction. The solidphase may be in any form useful for carrying out the particularreaction, including particles, beads, rods, plates, fibers, filters,etc. Methods for attaching organometallic catalysts to solid supportsand using them in metathesis reactions are known in the art. One methodfor attaching the preferred monomeric catalyst of the present inventionto a polymer substrate is described in Example 19.

[0065] The catalysts of the present invention can be immobilized withretention of all the ligand environment characteristics responsible forits high activity. In one embodiment, the immobilized catalyst isimmobilized on the solid support in a manner such that the support is acatalyst carrier. In this embodiment, the metathesis substrate releasesthe active metal carbene from the polymer, the complex promotes severalcycles in solution, and is again trapped by the support so that it canbe easily retrieved and reused. In other words, the present immobilizedcatalyst systems combine the benefits of heterogeneous catalysis(recyclability) and homogeneous catalysis (high turnover).

[0066] In a preferred embodiment of the invention, the transition metalcatalysts are immobilized on solid phase surfaces such as, for example,metals, glass, polymers, ceramics, organic polymer beads, inorganicsol-gels and other inert substances, without impairing their ability tocatalyze various forms of metathesis reactions in a highly efficientmanner. In a currently preferred embodiment, the solid phase is aninorganic sol gel such as, for example, a glass monolithic gel.

[0067] The surface immobilization of the catalysts to solid phasesubstrates involves a preliminary step wherein the catalysts arechemically reacted with an organic coupling agent to provide adductsthat are capable of chemically bonding to said solid phase substrates.In a preferred embodiment, the said adduct contains a silylfunctionality that enables surface immobilization on solid phasesubstrates via chemical bonding of the silyl group to the saidsubstrates. In a most preferred embodiment the catalysts of theinvention are coupled to the organic linker and functionalized with asilane-containing moiety in a single step. Surface immobilization of thesaid silane modified compounds onto solid phase substrates isaccomplished in-situ by subsequent addition of said substrate into thereaction vessel. Preferred coupling agents are norbornene derivativesthat are capable of reacting with catalysts of the invention, andfurther capable of reacting with organo-silane agents to providesilyl-functionalized derivatives that may be used in surfaceimmobilization reactions. Preferred solid phase substrates include thosecapable of chemically reacting with the silyl moiety. In a mostpreferred embodiment, the solid phase substrate is a porous glassmonolith having preferably an average pore size of about 200 Å. Morespecifically, as shown in FIG. 4, a ring-opening reaction combined withcross metathesis of anti-norbornenol ester 35 in with 1.0 equivalenteach of organometallic complex 4 and allylchlorodimethylsilane (0.05 MCH₂Cl₂, 22° C.) proceeds to >98% conversion in <1 h to give adduct 36(analyzed by 400 MHz ¹H NMR). Surface immobilization of adduct 36 isaccomplished by adding a pre-weighed batch of vacuum-dried sol-gelmonoliths such as, for example, glass monolithic gel with about 200 Åpore size to the reaction mixture, followed by stirring for 96 h at 40°C. After extensive washing with CH₂Cl₂ and drying in vacuo, bright greenglass pellets of surface immobilized catalyst 37 are recovered.

[0068] In other preferred embodiments, surface immobilized catalysts 38and 39 shown in Scheme 7 are obtained in an analogous fashion from thecorresponding norbornene substrates. Surface immobilized catalysts 35,36 and 37 were evaluated for catalytic activity, recovery andrecyclability.

[0069] All surface immobilized catalysts of the present invention showgood activity in catalyzing metathesis reactions. Table 4 showsefficiency of immobilized catalysts 37, 38 and 39 carried throughiterative rounds of ring-closing metathesis (RCM) of acrylic amide 40 toyield 41. The catalyst loading for each of these transformations wasdetermined by the mass increases that accompany functionalization of thegel surface. Relative reaction rates of three catalysts were assessed bystopping the reaction prematurely during the third round of RCM, at apoint where TLC analysis still showed the presence of a small amount ofstarting material. Spectroscopic analysis of the (400 MHz ¹H NMR)unpurified reaction mixture (97-100% conversion, Round 3, Table 4)indicates that reaction efficiency of all three catalysts tested areequivalent. TABLE 4 Utility of Immobilized Catalysts in catalyzing RCM

Catalyst Round 1 (3 h) Round 2 (3 h) Round 3 (2 h) Round 4 (3 h) MetalLoss 37 >98% conv, 99% >98% conv, 100% 97% conv, 100% >98% conv, 99% 1.8mg(25%) 38 >98% conv, 100% >98% conv, 100% 97% conv, 99% >98% conv, 100%1.9 mg(20%) 39 >98% conv, 99% >98% conv, 99% 99% conv, 100% >98% conv,100% 1.6 mg(22%)

[0070] The surface immobilized catalysts of the present inventionprovide the following advantages over non-immobilized catalysts 1 and 2and 2a (FIG. 3).

[0071] (1) In contrast to reactions run with 5 mol % non-immobilizedcatalysts 1 and 2, the proton NMR spectra of the unpurified reactionmixtures in every case consists of >98% pure cyclo-olefin (analyzed by400 MHz ¹H NMR); no catalyst or byproduct thereof is detected).Concentration of the reaction mixtures consistently deliver thecyclo-olefins as an off-white solids in >98% yield. These materials meetthe acceptance criteria as defined by CH combustion analysis withoutneed for purification.

[0072] (2) No post reaction filtration step is required for productisolation and catalyst recovery. The reaction mixture is removed bypipetting, decantation or pumping, following which the solid surface(for example, inorganic gel pellets such as glass) with the immobilizedcatalyst is washed with CH₂Cl₂, prior to addition of fresh substrate fora subsequent metathesis reaction.

[0073] (3) After four consecutive rounds of RCM utilizing surfaceimmobilized catalysts with different organic linker types, therespective gel pellets after thorough drying in vacuo and subsequentweighing yielded mass differences that are highly reproducible,indicating a net metal loss of between 20 to 25% over the four reactioncycles. Despite this significant drop in Ru catalyst loading relative tothe initial values, the catalytic activities of the recovered, recycledgel pellets remain high. Absence of cross-contamination of reactionproducts by surface immobilized catalysts of the present invention maybe demonstrated by using the same samples for the ring-openingmetathesis (ROM) of 7-anti-norbornenol in the presence of a variety ofdonor olefins, including highly electron-rich olefins such asvinylferrocene. As shown in Table 5, productive metathesis for threeadditional rounds of norborneol 42 occurred in <1 h to yield ring-openedcompound 43. The Ru-containing impurities, as well as the product of theprevious RCM reaction 39 could not be detected by NMR spectroscopy (400MHz ¹H NMR analysis) of the corresponding unpurified reaction productmixtures. TABLE 5 Efficiency of Recycled Catalysts in catalyzing ROCM

R = Ph R = n-hexyl R - Ferrocene Catalyst Rounds 5 (40 min) Round 5 (40min) Round 7 (40 min) 37 >98% conv >98% conv >98% conv 38 >98% conv >98%conv >98% conv 39 >98% conv >98% conv >98% conv

[0074] In addition to attaching the catalyst to a substrate such as anorganic polymer bead that necessitates an additional filtration step toisolate the product from catalyst, the catalysts of the invention may beimmobilized on the surface of a reaction vessel. In a preferredembodiment, the catalyst metal complex is immobilized to an integralpart of the reaction apparatus itself, for example, a glass round-bottomreaction flask, a magnetic stir bar, or other component used to carryout the reaction. Catalysts of the present invention may also beattached to highly porous glass monoliths, which can be synthesized andmanipulated from readily available materials.

[0075] Preferably, the linker moiety used to bind the metal complex tothe solid support should be chemically inert under the reactionconditions and form a non-labile link between the metal complex andsupport. In one embodiment, as shown in Scheme 7, the present catalystsare immobilized using a procedure that allows incorporation of both thelinker and the active metal complex in a single step. Subsequentdiffusion of the catalyst and linker into the pores of a sol gelmaterial, for example, results in a substitution reaction involving thelabile Si-Cl bond with free hydroxyl groups on the glass surface,thereby immobilizing the catalyst to the glass surface.

[0076] As shown in Example 19, ring-opening cross metathesis (0.10 mmolscale) of a strained olefin using the catalyst synthesized according toExample 4 (shown as Formula 3 in Equation 1 above) proceeded to >98%conversion. In this reaction, a catalyst of the present invention wasimmobilized on a single 50 mg sol gel monolith. After extensive washingand drying in vacuo, a bright green glass pellet was recovered whichshowed good activity in the RCM of the terminal diene (0.10 mmol scale).The immobilized catalyst was carried through three iterative rounds ofmetathesis.

[0077] The following Examples are provided to illustrate the presentinvention, and are not intended to be limiting in any way.

EXAMPLES

[0078] General. Infrared (IR) spectra were recorded on a Perkin-Elmer781 spectrophotometer, λmax in cm⁻¹. Bands are characterized as broad(br), strong (s), medium (m), and weak (w). ¹H NMR spectra were recordedon Varian Unity 300 (300 MHz), Gemini 2000 (400 MHz), or INOVA 500 (500MHz) spectrometers. Chemical shifts are reported in ppm fromtetramethylsilane with the solvent resonance as the internal standard(CDCl₃): δ7.26 ppm; CD₃CN: δ1.94 ppm). Data are reported as follows:chemical shift, multiplicity (s=singlet, d=doublet, t=triplet, br=broad,m multiplet), coupling constants (Hz), integration, and assignment. ¹³CNMR spectra were recorded on Varian Unity 300 (75 MHz), Gemini 2000 (100MHz), or INOVA 500 (125 MHz) spectrometers with complete protondecoupling. Chemical shifts are reported in ppm from tetramethylsilanewith the solvent as the internal reference (CDCl₃: 77.00 ppm; CD₃CN:1.19 ppm). ³¹P NMR spectra were recorded on a Varian Gemini 2000 (162MHz) spectrometer with complete proton decoupling. The chemical shiftsof the phosphorus resonances were determined relative to phosphoric acidas an external standard (H₃PO₄: δ0.0 ppm).

[0079] All reactions were carried out under an atmosphere of dry Ar inoven—(135° C.) and flame-dried glassware with standard Schlenk orvacuum-line techniques. In most instances, solid organometalliccompounds were purified and recovered in air and later stored in adrybox under an atmosphere of argon. (PCy₃)Cl₂RuCHPh (Formula 2) wasprepared according to literature procedures.³⁰ (4,5-dihydrolMES) (PCy₃)Cl₂Ru═CHPh (Formula 3) and its requisite starting materials wereprepared by a modification of the published method³ (see below forfurther details). 2-isopropoxystyrene was prepared by alkylation andWittig olefination. All other materials were obtained from commercialsources and purified before use. Tetrahydrofuran, diethyl ether,benzene, and toluene were distilled from sodium metal/benzophenoneketyl. Dichloromethane, pentane, hexanes, 2-propanol, triethylamine, andethanol were distilled from calcium hydride under Ar. Methanol wasdistilled over Mg under Ar. 2,4,6-trimethylaniline was vacuum distilled.Triethyl orthoformate (Aldrich) was distilled from MgSO₄ under reducedpressure. 3-(4-Hydroxyphenyl)-propionic acid (Aldrich) wasrecrystallized from water. 2-lodopropane (Aldrich) was distilled fromMgSO₄ under argon. Dimethylformamide (Fisher) was stored over 4Amolecular sieves prior to use. Tributyl(vinyl)tin (Aldrich) was vacuumdistilled from MgSO₄. Allylmagnesium bromide was freshly prepared fromdistilled allyl bromide (Aldrich) and Mg turnings (Strem) and titratedbefore use. Silicon tetrachloride (Strem) was distilled under argon.Chlorodimethylsilane (Aldrich) was distilled under argon.9-Borabicyclo[3.3.1]nonane (9-BBN) was freshly prepared from distilled1,5-cyclooctadiene (Aldrich), borane-dimethylsulfide complex (Aldrich),and anhydrous dimethoxyethane (Aldrich, distilled from sodiummetal/benzophenone ketyl).³² 4-Dimethylaminopyridine (DMAP) (Aldrich)was recrystallized from anhydrous toluene. The following materials werepurchased from commercial sources and used as received: glyoxal (40% wt.soln in water) (Aldrich), sodium cyanoborohydride (Aldrich), bromocresolgreen (Fisher), ammonium tetrafluoroborate (Aldrich), potassiumtert-butoxide (Strem), copper(I) chloride (Strem), anhydrous HCl(Aldrich), sodium hydride (Aldrich), bromine (Aldrich), acetic acid(Fisher), sodium thiosulfate (Aldrich), 2,6-di-tert-butyl-4-methylphenol(Aldrich), tetrakis(triphenylphosphine)palladium (0) (Strem), activatedcarbon (Aldrich), chloroplatinic acid hexahydrate (Speier's catalyst)(Strem), platinum-divinyltetramethylsiloxane complex in xylene(Karstedt's catalyst) (Geleste), hydrogen peroxide (30% wt. soln inwater) (Aldrich), citric acid (Aldrich), and1-(3-dimethylaminopropyl)-3-ethyl carbodimide (EDC) (Advanced Chemtech).

[0080] All silica gel column chromatography was driven with compressedair and performed with silica gel 60 (230-400 mesh; pH (10% suspension)6.5-7; surface area 500 m²/g; pore volume 0.75 ml/g) obtained from TSIChemical Co. (Cambridge, Mass.). Similar to the original monomer 1,dendritic catalyst 30 forms a dark brown solution in organic solvents.In contrast, the more active catalysts bearing the 4,5-dihydrolMESligand form bright green-colored organic solutions. The purification ofthe above complexes can be easily monitored visually since they appearas dark brown or green-colored bands on the column. Dendritic complexes30 and 31 are significantly more polar than the corresponding monomers.Following a metathesis reaction mediated by 30 or 31, isolation of bothproduct and catalyst typically involved simply a filtration of the crudemixture through a silica gel plug in 100% CH₂Cl₂ followed by a column“flush” in 100% Et₂O (TLC Rf of 30 and 31<1.0 in CH₂Cl₂).

Example 1 Synthesis of ((2,4,6-Trimethylphenyl)NCH)₂

[0081] Glyoxal (3.73 mL of a 40% weight solution in water, 32.5 mmol)was dissolved in 325 mL of reagent-grade methanol in a 500 mL flask.2,4,6-Trimethylaniline (8.25 mL, 58.8 mmol, 1.81 equiv) was addeddropwise to this solution by syringe. The mixture was stirred for 12 hat 22° C. as a bright yellow precipitate slowly formed. The mixture wasdiluted with CH₂Cl₂, dissolving the solid. The resulting yellow solutionwas dried over MgSO₄, filtered, and concentrated to a yellow-orangesolid residue. The unpurified product was recrystallized from anhydrousmethanol (for every 10 g, 850-900 mL of MeOH was required for completedissolution at reflux). After slow cooling to 22 EC followed bysubsequent storage of the sample at −20° C. for 12 h, long canary yellowcrystals formed. The product was recovered by vacuum filtration, washedwith pentane, and dried under high vacuum (7.40 g, 25.3 mmol, 86%). IR(NaCl): 3005 (m), 2946 (s), 2916 (s), 2854 (m), 2725 (w), 1617 (s), 1595(w), 1476 (m), 1438 (w), 1374 (m), 1265 (m), 1202 (s), 1141 (m), 1031(w), 850 (s), 780 (m), 739 (s), 705 (w), 609 (w). ¹H NMR (400 MHz,CDCl₃): 8.12 (s, 2H, NCH), 6.93 (s, 4H, aromatic CH), 2.31 (s, 6H,mesityl p-CH₃), 2.18 (s, 12H, mesityl o-CH₃). ¹³C NMR (100 MHz, CDCl₃):δ163.31, 147.29, 134.13, 128.86, 126.44, 20.83, 18.28. HRMS Calcd forC₂₀H₂₃N₂: 292.1861 (M-H)⁺. Found: 291.1862. Anal. Calcd for C₂₀H₂₄N₂: C,82.15; H 8.27.Found: C, 81.99; H, 8.12.

Example 2 Synthesis of ((2,4,6-Trimethylphenyl)NHCH₂)₂

[0082] The bis(imine) ((2,4,6-trimethylphenyl)NCH) (7.30 g, 25.0 mmol)was suspended in 250 mL of MeOH in a 500 mL round-bottom flask. Severalcrystals of bromocresol green were added as a pH indicator and themixture was cooled to 0° C. NaCNBH₃ (10.0 g, 159 mmol, 6.4 equiv) wasadded to the reaction mixture in one portion as a solid. Vigorousbubbling was observed and the reaction mixture turned a deep blue-greencolor (alkaline pH). After 10 mm concentrated HCl was added dropwise tothe mixture, restoring its original yellow color. Additional reductionslowly occurred, causing the mixture to again become basic. Theacidification process was repeated (typically two more times) until theyellow color persisted. The reaction mixture was warmed to 22° C. andstirred for 1 h. A solution of 2 M KOH was added dropwise until themixture was weakly alkaline (pH=8-9). The mixture was then diluted withwater (300 mL), transferred to a separatory funnel, and washed threetimes with Et₂O (500 mL). The combined organic layers were washed with800 mL of saturated solution of sodium chloride, dried over MgSO₄,filtered, and concentrated into a yellow oil. Silica gel chromatography(TLC Rf=0.32 in 4:1 pentane: Et₂O) afforded the product as a colorlessoil (7.13 g, 24.1 mmol, 96%). IR (NaCl): 3367 (br), 2996 (s), 2916 (s),2854 (s), 2729 (w), 1612 (w), 1485 (s), 1446 (s), 1373 (m), 1344 (w),1228 (s), 1207 (m), 1154 (m), 1110 (m), 1062 (w), 1030 (m), 1012 (m),853 (s), 822 (w), 801 (w), 738 (m), 563 (m). ¹H NMR (400 MHz, CDCl₃):δ6.85 (s, 4H, aromatic CH), 3.30 (br, 21-1, NH), 3.17 (s, 4H, NCH₂CH₂N),2.30 (s, 12H, mesityl o-CH₃), 2.25 (s, 6H, mesitylp-CH₃). ¹³C NMR (100MHz, CDCl₃): δ143.24, 131.35, 129.65, 129.38, 49.19, 20.60, 18.50. HRMSCalcd for C₂₀H₂₈N₂: 296.2252 Found: 296.2258. Anal. Calcd for C₂₀H₂₈N₂:C, 81.03; H, 9.52. Found: C, 81.28; H, 9.41.

Example 3 Synthesis of 1,3-Dimesitylimidazolinium Tetrafluoroborate

[0083] A 25 mL round-bottom flask was charged with((2,4,6-trimethylphenyl)NHCH₂)₂ (7.81 g, 26.4 mmol) and ammoniumtetrafluoroborate (2.77 g, 26.4 mmol, 1.0 equiv). Triethylorthoformate(4.39 mL, 26.4 mmol, 1.0 equiv) was added by syringe. The flask wasequipped with a reflux condenser and submerged into a preheated oil bathat 120° C. The mixture was refluxed for 3 h and cooled to 22° C. Atan-colored solid precipitated, leaving a cloudy suspension. Thismixture was recrystallized from hot anhydrous ethanol. The resultingbright white crystals of product were recovered by vacuum filtration,washed with pentane, and dried under high vacuum (5.62 g, 14.3 mmol,54%). Additional product could be obtained by further recrystallizationof the mother liquor. IR (NaCl): 3091 (w), 2979 (br), 2941 (br), 1633(s), 1487 (w), 1459 (w), 1393 (w), 1313 (w), 1269 (m), 1214 (w), 1092(m), 1054 (s), 1036 (s), 965 (w), 880 (w), 852 (m). ¹H NMR (400 MHz,CD₃CN): δ8.14 (s, 1H, NCHN), 7.08 (s, 4H, aromatic CH), 4.43 (s, 4H,NCH₂CH₂N), 2.37 (s, 12H, mesityl o-CH₃), 2.32 (s, 6H, mesityl p-CH₃).¹³C NMR (100 MHz, CD₃CN): δ160.41 (d, ^(J)NC=10.3 Hz), 141.54, 136.50,131.36, 130.61, 52.21, 21.16, 17.92. HRMS Calcd for C₂₁H₂₇N₂: 307.2174(cation only). Found: 307.2175. Anal. Calcd for C₂₁H₂₇BF₄N₂: C, 63.97; H6.90. Found: C, 63.79; H, 6.85.

Example 4 Synthesis of (4,5-dihydrolMES) (PCy₃)Cl2Ru═CHPh (Formula 3)

[0084] The ligand salt 1,3-dimesitylimidazolinium tetrafluoroborate(2.94 g, 7.46 mmol, 1.2 equiv) was suspended in 50 mL of THF in a 250 mLround-bottom flask. This mixture was then treated with a solution ofpotassium tert-butoxide (840 mg, 7.49 mmol, 1.2 equiv) in 50 mL of THFvia cannula at 22 EC. This mixture was immediately cannula transferred(20 mL THF used as rinse) to a second vessel containing a solution of(PCy₃)Cl₂Ru═CHPh (2) (5.01 g, 6.09 mmol, 1.0 equiv) in 100 mL of benzene(additional stirring of the ligand salt mixture at 22° C. prior toexposure to the Ru-carbene often resulted in incomplete conversion tothe desired product). The resulting mixture was refluxed at 80 EC for 30mm and then cooled to 22° C. All manipulations from this point forwardwere carried out in air with reagent-grade solvents. The solvents wereremoved at reduced pressure, leaving a red-brown solid residue. Thecrude residue was dissolved in a minimal volume of 9:1 hexanes: Et₂O andloaded onto a wide plug of silica gel. Elution with the same solventsystem slowly removed a pink-red band of the desired product from thecolumn. Concentration of the product fractions in vacuo removed the morepolar and volatile Et₂O and resulted in spontaneous precipitation of thecatalyst from hexanes as a cranberry red, microcrystalline solid (3.78g, 4.45 mmol, 73%). These crystals were dried under high vacuum. IR(NaCl): 3057 (m), 3039 (m), 3015 (m), 2927 (s), 2850 (s), 1608 (w), 1479(s), 1446(s), 1421 (s), 1380 (m), 1328 (w), 1266 (s), 1243 (m), 1205(w), 1174 (m), 1129 (w), 1036 (w), 1005 (m), 909 (m), 849 (m), 737 (s),703 (m), 687 (m), 624 (w), 578 (w). ¹H NMR (300 MHz, CDCl₃): δ19.13 (s,1H, Ru═CHAr), 7.35 (dd, J=7.8, 7.0 Hz, 2H, aromatic CH), 7.09 (m, 3H,aromatic CH), 7.01 (s, 4H, mesityl aromatic CH), 3.98 (s, 4H, N(CH₂)₂N),2.80-0.70 (m, 33H, P(C₆H₁₁)₃), 2.31 (s, 12H, mesityl o-CH₃), 1.90 (s,6H, mesitylp-CH₃). ¹³C NMR (75 MHz, CDCl₃): δ293.40, 220.29 (d,^(J)CN=76.2 Hz), 151.16, 151.11, 138.27, 137.49, 137.08, 135.06, 129.77,127.78, 51.64 (d, ^(J)CN=71.9 Hz), 31.30 (d, ^(J)PC=15.6 Hz), 27.68 (d,=9.8 Hz), 26.07, 21.09, 20.86, 19.88. ³¹P NMR (162 MHz, CDCl₃): δ161.90(s, PCy₃). Anal. Calcd for C₄₆H₆₅Cl₂N₂PRu: C, 65.08; H, 7.72. Found: C,65.18; H, 7.71.

Example 5 Synthesis of (4,5-dihydrolMES)Cl₂Ru═CH-o-O-i-Pr C₆ H₄ (Formula5)

[0085] (4,5-dihydrolMES) (PCy₃)Cl₂Ru═CHPh (formula 3) (895 mg, 1.05mmol, 1.03 equiv) and CÜCl (261 mg, 2.64 mmol, 2.59 equiv) were weighedinto a 100 mL round-bottom flask in a glove box and dissolved in 20 mLof CH₂Cl₂. 2-isopropoxystyrene (4) (166 mg, 1.02 mmol, 1.0 equiv) wascannulated into the resulting deep red solution in 20 mL of CH₂Cl₂ at22° C. The flask was equipped with a condenser and stirred at reflux for1 h. From this point forth, all manipulations were carried out in airwith reagent-grade solvents. The reaction mixture was concentrated invacuo to a dark brown solid residue. The crude material was dissolved ina minimal volume of 2:1 pentane: CH₂Cl₂ and loaded onto a plug of silicagel. Elution with 2:1 pentane: CH₂Cl₂ and then 1:1 pentane: CH₂Cl₂removed a bright green band from the column. The column was then washedsuccessively with straight CH₂Cl₂ and Et₂O (light green/yellow bandselute). These three fractions were pooled and concentrated to a darkgreen solid. This material was passed through a second silica gel plugin 1:1 hexanes:CH₂Cl₂ (bright green band elutes). Subjection to reducedpressure removed the more volatile CH₂Cl₂ from the product solution andresulted in spontaneous precipitation of the catalyst from hexanes as abright green crystalline solid; drying under high vacuum afforded 635 mg(1.01 mmol, 99%) of the desired product. IR (NaCl): 2922 (br), 2853 (m),1730 (w), 1606 (w), 1589 (m), 1575 (w), 1478 (s), 1452 (s), 1420(s),1397 (m), 1384 (m), 1295 (m), 1263 (s), 1217 (m), 1160(w), 1113 (s),1098 (w), 1035 (w), 938 (m), 852 (w), 801 (w), 746 (m), 737 (m), 580(m). ¹H NMR (400 MHz, CDCl₃): δ16.56 (s, 1H, Ru═CHAr), 7.48 (m, 1H,aromatic CH), 7.07 (s, 4H, mesityl aromatic CH), 6.93 (dd, J=7.4, 1.6Hz, 1H, aromatic CH), 6.85 (dd, J=7.4, 7.0 Hz, 1H, aromatic CH), 6.79(d, J=8.6 Hz, 1H, aromatic CH), 4.90 (septet, J=6.3 Hz, 1H,(CH₃)₂CHOAr), 4.18 (s, 4H, N(CH₂)₂N), 2.48 (s, 12H, mesityl o-CH₃), 2.40(s, 6H, mesityl p-CH₃), 1.27 (d, J=5.9 Hz, 6H, (CH₃)₂CHOAr). ¹³C NMR(100 MHz, CDCl₃): 6296.83 (q, J=61.5 Hz), 211.13, 152.04, 145.13 (d,Joc=3.9 Hz), 145.09, 138.61, 129.39 (d, ^(J)NC=3.9 Hz), 129.35, 129.17,122.56, 122.11, 112.75, 74.86 (d, ^(J)oc=10.7 Hz), 51.42, 30.86, 25.93,21.08. HRMS Calcd for C₃₁H₃₈Cl₂N₂O⁹⁹Ru: 623.1421 Found: 623.1411. Anal.Calcd for C₃₁H₃₈Cl₂N₂ORu: C, 59.42; H, 6.11; Cl, 11.32; N, 4.47. Found:C, 59.28; H, 6.35; Cl, 11.36; N, 4.12.

Example 6 Synthesis of Isopropyl-1-(p-hydroxyphenyl)propionate

[0086] Through a stirring solution of 3-(4-hydroxyphenyl) propionic acid(24) (5.00 g, 30.1 mmol) in 2-propanol (167 mL, 72.0 equiv) was bubbledanhydrous HCl for 50 mm. The flask was sealed under Ar and stirred for12 h at 22° C. The solvent was removed under reduced pressure withgentle heating, leaving a thick, colorless oil. Removal of residual2-propanol under high vacuum at 22° C. resulted in spontaneousprecipitation of the desired product as a bright white crystalline solid(6.12 g, 29.4 mmol, 98%). IR (NaCl): 3412 (br), 3024 (w), 2981 (m), 2930(w), 2873 (w), 1712 (m), 1613 (s), 1595 (m), 1519 (s), 1449 (m), 1377(s), 1298 (m), 1266 (s), 1225 (s), 1149 (m), 1108 (s), 904 (m), 837 (m),820 (m), 609 (m). ¹H NMR (400 MHz, CDCl₃): δ7.04 (d, J 8.4 Hz, 2H,aromatic CH), 6.74 (d, J=8.4 Hz, 2H, aromatic CH), 5.80 (s, 1H, ArOH),5.00 (septet, J=6.3 Hz, 1H, (CH₃)₂CHO), 2.87 (t, J=7.6 Hz, 2H,CH₂CO₂iPr), 2.57 (t, J=7.6 Hz, 2H, ArCH₂), 1.20 (d, J=6.3 Hz, 6H,(CH₃)₂CHO). ¹³C NMR (100 MHz, CDCl₃): δ172.97, 154.04, 132.19, 129.28,115.19, 68.07 (d, Joc=9.8 Hz), 36.64, 30.23, 21.85. HRMS Calcd forC₁₂H₁₆O₃: 208.1099. Found: 208.1099. Anal. Calcd for C1₂HI₆03: C, 69.21;H, 7.74. Found: C, 69.43; H, 7.88.

Example 7 Synthesis of Isopropyl-1-(p-isopropoxyphenyl)propionate (25)

[0087] A solution of isopropyl-1-(p hydroxyphenyl)propionate (0.822 g,3.95 mmol) in THF (10 mL) was treated via cannula with a suspension ofsodium hydride (104 mg, 5.92 mmol, 1.1 equiv) in THF (10 mL) at 0° C.After gas evolution had subsided, DMF (20 mL) and 2-iodopropane (0.40mL, 4.0 mmol, 1.0 equiv) were syringed into the reaction mixture. Theresulting suspension was stirred at 22° C. for 6 hours, at which timeadditional sodium hydride (71.0 mg, 2.96 mmol. 0.75 equiv) in THF (5 mL)and 2-iodopropane (0.30 mL, 3.0 mmol, 0.75 equiv) were added. Thisprocedure was repeated if necessary until no starting material could bedetected by TLC analysis (we suspect that competing elimination of theelectrophile is responsible for incomplete product conversions,requiring us to resubject the reaction mixture). The mixture was thendiluted with Et₂O (150 mL) and water (200 mL) and transferred to aseparatory funnel. The organic layer was removed, and the aqueous layerwas washed twice with Et₂O (100 mL). The combined organic layers werewashed with three volumes of water to remove residual DMF. The organicsolution was then dried over MgSO₄, filtered, and concentrated in vacuoto a pale yellow oil. The product was passed through a short column ofsilica gel in 7:1 hexanes:Et₂O affording 811 mg (3.24 mmol, 82%) of acolorless oil (TLC Rf=0.30 in 7:1 hexanes:Et₂O). IR (NaCl): 2978 (m),2934 (w), 1731 (s), 1612 (w), 1510 (s), 1452 (w), 1383 (m), 1295 (w),1242 (s), 1182 (m), 1109 (s), 957 (w), 829 (w). ¹H NMR (400 MHz, CDCl₃):δ7.09 (d, J=8.6 Hz, 2H, aromatic CH), 6.80 (d, J=8.6 Hz, 2H, aromaticCH), 5.00 (septet, J=6.3 Hz, 1H, (CH₃)₂CHO₂C), 4.50 (septet, J=6.3 Hz,1H, (CH₃)₂CHOAr), 2.87 (t, J=7.8 Hz, 2H, CH₂CO₂iPr), 2.55 (t,J=7.8 Hz,2H, ArCH₂), 1.32 (d, J=6.3 Hz, 6H, (CH₃)₂CHOAr), 1.20 (d, J=6.3 Hz, 6H,(CH₃)₂CHO₂C). ¹³C NMR (100 MHz, CDCl₃): 67 172.39, 156.12, 132.43,129.15, 115.81, 69.86 (d, J_(OC)=3.4 Hz), 67.59 (d, J_(OC)=9.8 Hz),36.59, 30.26, 22.14, 21.88. HRMS Calcd for C₁₅H₂₂O₃: 250.1569. Found:250.1566. Anal. Calcd for C₁₅H₂₂ _(O) ₃:C, 71.97; H, 8.86. Found: C,72.26; H, 9.04.

[0088] Example 8

Synthesis of Isopropyl-1-(m-bromo-p-isopropoxyphenyl)propionate.

[0089] A 50 mL round-bottom flask was charged withisopropyl-1-(p-isopropoxyphenyl)propionate (25) (1.09 g, 4.34 mmol) andCH₂C1₂ (20 mL, 0.20 M). 10 mL of acetic acid (0.18 mmol) was added tothe solution. Bromine (0.235 mL, 4.56 mmol, 1.05 equiv) was then slowlyadded dropwise via syringe, forming a red-colored solution. Over thecourse of 0.5 h, the solution gradually turned a pale yellow color asthe bromine was consumed. After 1 h the reaction was quenched with 5 mLof saturated sodium thiosulfate. The mixture was diluted with water (200mL) and Et₂O (200 mL) and partitioned in a separatory funnel. Theaqueous layer was washed with 2×150 mL of Et₂. The combined organiclayers were dried over MgSO₄, filtered, and concentrated to a yellowoil. This material could be purified by vacuum distillation or silicagel chromatography (TLC R_(f)=0.23 in 10:1 hexanes:Et₂O) to deliver theproduct as a colorless oil (1.40 g, 4.25 mmol, 98%). Crucial to thesuccess of this reaction is this use of exactly 1.0-1.1 equiv ofbromine; an excess of the reagent leads to dibrominated adducts. Ifthese impurities are generated, a CH₂Cl₂/pentane solvent system must beused as eluant to effect purification of the desired product on silicagel (TLC R_(f)=0.30 in 3:2 CH₂Cl₂:pentane). The halogenated solvent mixalso promotes a facile separation of the product and the startingmaterial (25) in the event that the reaction does not proceed tocompletion (<1.0 equiv Br₂). IR (NaCl) 2979 (m), 2936 (w), 1729 (s),1604 (w), 1493 (s), 1384 (m), 1373 (m), 1281 (m), 1253 (s), 1240 (m),1180 1140 (m), 1109 (s), 1046 (w), 954 (m), 812 (w). ¹H NMR (400 MHz,CDCl₃): δ7.38 (d, J=2.2 Hz, 1H, aromatic CH), 7.06 (dd, J=8.4, 2.2 Hz, 1H, aromatic CH), 6.83 (d, J=8.4 Hz, 1H, aromatic CH), 4.96 (septet,J=6.2 Hz, 1 H, (CH₃)₂CHO₂C), 4.50 (septet, J=6.2 Hz, 1H, (CH₃)₂CHOAr),2.85 (dd, J=7.7, 7.3 Hz, 2H, CH₂CO₂iPr), 2.55 (dd, J=7.7, 7.3 Hz, 2H,ArCH₂), 1.36 (d, J=5.9 Hz, 6H, (CH₃)₂CHOAr), 1.20 (d, J=6.6 Hz, 6H,(CH₃)₂CHO₂C). ¹³C NMR (100 MHz, CDCl₃): δ172.06, 152.84, 134.36, 133.09(d, J_(OC)=7.3 Hz), 128.03, 115.98, 113.63, 72.34 (d, J_(OC)=3.9 Hz),67.80 (d, J_(OC)=12.2 Hz), 36.29, 29.90, 22.15 (d, J_(OC)2.4 Hz), 21.89(d, J_(OC) 3.4 Hz). HRMS Calcd for C₁₅H₂₁BrO₃: 328.0674. Found:328.0671. Anal. Calcd for C₁₅H₂₁BrO₃: C, 54.72; H, 6.43. Found: C,54.84; H, 6.43.

Example 9 Synthesis ofIsopropyl-1-(p-isopropoxy-m-vinylphenyl)propionate

[0090] Pd(PPh₃)₄ (166 mg, 0.144 mmol, 3 mol %) and2,6-di-tert-butyl-4-methylphenol (1 mg, 0.005:mmol) were weighed into a50 mL pear-shaped flask in a glove box and dissolved in 25 mL of drytoluene. This solution was transferred through a cannula into a neatsample of isopropyl-1-n-bromo-p-pisopropoxyphenyl)propionate (1.58 g,4.79 mmol) in a 50 mL round-bottom flask. The resulting pale yellowsolution was stirred for 15 mm at 22 EC. Tributyl(vinyl)tin (1.54 mL,5.27 mmol, 1.1 equiv) was then added dropwise to the reaction mixturethrough a syringe. The flask was equipped with a condenser and heated at110° C. for 12 h. As the reaction progressed, a shiny mirror-like filmof Bu₃SnBr salts was gradually deposited on the walls of the flask.After cooling to 22° C., the reaction mixture was passed through a smallplug of celite and activated carbon using Et₂O as the eluant andconcentrated in vacuo to give a yellow oil. Purification by silica gelchromatography (TLC R_(f)=0.27 in 8:1 hexanes:Et₂O) afforded 888 mg of acolorless oil (3.22 mmol, 67%). IR (NaCl): 2978 (s), 2936 (m), 2873 (w),1731 (s), 1627 (w), 1491 (s), 1373 (m), 1246 (s), 1180 (m), 1109 (s),996 (w), 957 (m), 904 (w), 814 (w). ¹H NMR (400 MHz, CDCl₃):6 7.31 (d,J=2.3 Hz, 1H, aromatic CH), 7.07-6.99 (m, 2H, aromatic CH and ArCHCH₂),6.80 (d, J8.2 Hz, 1H, aromatic CH), 5.71 (dd, J=17.8, 1.6 Hz, 1H,ArCHCH₂), 5.22 (dd, J=11.3, 1.6 Hz, LH, ArCHCH₂), 5.00 (septet, J=6.3Hz, 1H, (CH₃)₂CHO₂C), 4.49 (septet, J=6.3 Hz, 1H, (CH₃)₂CHOAr), 2.88(dd, J=7.8, 7.4 Hz, 2H, CH₂CO₂iPr), 2.57 (dd, J=8.2, 7.4 Hz, 2H, ArCH₂),1.33 (d, J=6.3 Hz, 6H, (CH₃)₂CHOAr), 1.21 (d, J=6.3 Hz, 6H (CH₃)₂CHO₂C).¹³C NMR (100 MHz, CDCl₃): δ172.37, 153.50, 132.52, 131.81, 128.38,127.67, 126.21 (d, J_(OC) 5.4 Hz), 114.42, 113.76 (d, J_(OC)=8.3 Hz),70.01 (d J_(OC), 3.4 Hz), 67.64 (d, J_(OC) 11.2 Hz), 36.58, 30.40,22.28, 21.93. HRMS Calcd for C₁₇H₂₄O₃: 276.1725. Found: 276.1716. Anal.Calcd for C₁₇H₂₄O₃: C, 73.88; H, 8.75. Found: C, 73.71; H, 8.73.

[0091] Example 10

Synthesis of I-(p-isopropoxy-m-vinylphenyl)propionic acid (26)

[0092] A 100 mL round-bottom flask was charged withisopropyl-1-(p-isopropoxy-m-vinylphenyl)propionate (462 mg, 1.67 mmol)and 66.8 mL of 1 M KOH (66.8 mmol, 40 equiv). The reaction vessel wasequipped with a condenser and heated at 100° C. for 12 h. The mixturewas then diluted with 100 mL of water, transferred to a 500 mLErlenmeyer flask, and cooled to 0° C. The mixture was neutralized by thedropwise addition of ice-cold 1 M HCl. At a pH of ˜7, 150 mL of Et₂O wasadded. The aqueous layer was acidified further to pH 3-4 with vigorousstirring, resulting in spontaneous precipitation of the product thatimmediately enters the organic phase. The layers were partitioned in aseparatory funnel (an emulsion may form, requiring extended time forphase separation), and the aqueous layer was washed with additional Et₂O(150 mL). The pH of the aqueous layer was then lowered to ˜2 in thepresence of Et₂O. Again, the organic layer was collected and the aqueouslayer was washed. The organic layers were pooled and washed with 500 mLof a saturated solution of sodium chloride. Drying over MgSO₄ andconcentration in vacuo afforded 355 mg (1.52 mmol, 91%) of a lightyellow solid which proved to be >98% pure as judged by ¹H NMRspectroscopy (400 MHz). If necessary, the acid could be further purifiedby silica gel chromatography (TLC R_(f)=0.31 in 3:2 hexanes:Et₂O). It isrecommended that the above procedure be followed with care since theproduct is quite prone to acid-catalyzed polymerization of the styrenemoiety. Rapid, uncontrolled addition of the acid or acidification in theabsence of Et₂O can result in complete loss of the product topolymerization. IR (NaCl):2979 (m), 2935 (w), 2860 (w), 2760 (w), 1686(s), 1600 (s), 1243 (s). ¹H NMR (500 MHz, CDCl₃):δ11.26 (br, 1H, CO₂H),7.32 (d, J=2.3 Hz, 1 H, aromatic CH), 7.06-7.00 aromatic CH andArCHCH₂), 6.81 (d, J=8.5 Hz, 1H, aromatic CH), 5.72 (dd, J=17.8, 1.5 Hz,1H, ArCHCH₂), 5.23 (dd, J=11.0, 1.5 Hz, 1H, ArCHCH2), 4.50 (septet,J=6.1 Hz, 1H, (CH₃)₂CHOAr), 2.90 (dd, J=8.0, 7.6 Hz, 2H, CH₂CO₂iPr),2.67 (dd, J=8.0, 7.6 Hz, 2H, ArCH₂), 1.34 (d, J=6.2 Hz, 6H,(CH₃)₂CHOAr). ¹³C NMR (125 MHz, CDCl₃): δ178.78, 153.77, 132.13, 131.88,128.40, 127.87, 126.29, 114.48, 113.99, 70.99, 35.80, 29.88, 22.19. HRMSCalcd for C₁₄H₁₈O₃: 234.1256. Found: 234.1257. Anal. Calcd for C14H₁₈O₃:C, 71.77; H, 7.74. Found: C, 71.71; H, 7.68.

Example 11 Synthesis of Tetraallylsilane (27)

[0093] A 250 mL 2-neck flask equipped with a condenser and additionfunnel was charged with freshly prepared allylmagnesium bromide in Et₂O(92.3 mL of a 0.95 M solution, 87.7 mmol, 4.1 equiv). SiCl₄ (2.45 mL,21.4 mmol) slowly added to the solution of Grignard reagent through theaddition funnel in 20 mL of Et₂O at 22° C. over the course of 1 h. After12 h of reflux at 35° C., the reaction was cooled to 0° C. quenched with10 mL of a saturated solution of ammonium chloride. The mixture wasdiluted with water (200 mL) and Et₂O (100 mL) and transferred to aseparatory funnel. The organic 20 layer was collected and the aqueouslayer was washed with 2×150 mL of Et₂O. The organic layers were driedover MgSO₄, filtered, and concentrated in vacuo into a colorless oil.This material was passed through a small plug of silica in hexanes (TLCR_(f)=0.9 in hexanes) and concentrated. Vacuum distillation afforded3.33 g (17.3 mmol, 81%) of the product as a colorless oil. IR (NaCl):3078 (m), 3060 (w), 2996 (w), 2972 (m), 2916 (w), 2882 (w), 1630 (s),1419 (m), 1393 (m), 1195 (m), 1154 (m), 1037 (m), 991 (s), 930 (m), 893(s), 810 (m), ¹H NMR (400 MHz, CDCl₃): δ5.80 (ddt, J=16.8, 10.2, 8.2 Hz,4H, CH═CH₂), 4.94-4.87 (m, 8H, CH═CH₂), 1.61 (ddd, J=8.2, 1.4, 1.0 Hz,8H, SiCH₂). ¹³C NMR (100 MHz, CDCl₃): δ134.07, 113.93, 19.03. Anal.Calcd for C₁₂H₂₀Si: C, 74.92; H, 10.48. Found: C, 75.01; H, 10.32.

Example 12 Synthesis of Si[(CH₂)₃Si(Me)₂CH═CH_(2]4) (28)

[0094] A 0.1 M solution of H₂PtCl₆-6H₂O (Speier's catalyst)³⁴ wasfreshly prepared in anhydrous 2-propanol. The hydrosilylation could alsobe effected with Karstedt's catalyst.³⁵ A 25 mL round-bottom flask wascharged with the tetraene (27) (762 mg, 3.96 mmol), HMe₂SiCl (2.00 mL,18.0 mmol, 4.6 equiv, and THF (0.5 M, 8.0 mL). The platinum catalyst(10.0 mL, 0.010 mmol, 0.0025 equiv) was added dropwise by syringe andthe colorless solution was heated at reflux (65° C.) for 12 h. After 20mm of reaction, the mixture had turned dark green in color. Reactionprogress was monitored readily by thin-layer chromatography; thestarting material (TLC R_(f)=0.9 in hexanes) stains bright yellow withKMnO₄. Following the removal of solvent and excess silane in vacuo, ¹HNMR analysis (400 MHz) of the unpurified mixture indicated that <5% ofthe oc-substituted product was present and that the material wassufficiently pure for the subsequent alkylation step. Thus, the productwas dissolved in 20 mL of Et₂O and transferred by cannula into asolution of freshly prepared allylmagnesium bromide (0.936 M, 17.8 mL,16.7 mmol, 4.2 equiv). The reaction was stirred for 12 h at 22° C. andquenched with 10 mL of a saturated solution of ammonium chloride. Themixture was diluted with water (200 mL) and Et₂O (150 mL) andpartitioned in a separatory funnel. The aqueous layer was washed with2×100 mL of Et₂O. The combined organic layers were washed with a volumeof saturated sodium chloride, dried over MgSO₄, and vacuum filteredthrough a coarse frit funnel containing celite. Removal of volatilesgave a crude light orange oil which was purified by silica gelchromatography (TLC R_(f)=0.63 in hexanes). The product was recovered asa colorless oil (2.11 g, 3.56 mmol, 90%). IR (NaCl): 3077 (w), 2954 (m),2913 (s), 2876 (m), 1630 (m), 1418 (w), 1250 (s), 1153 (m), 1034 (w),932 (w), 893 (s), 844 (s), 698 (w), 629 (w). ¹H NMR (400 MHz, CDCl₃):δ5.78 (ddt J=16.8, 10.2, 8.2 Hz, 4H, CH═CH₂), 4.87-4.79 (m, 8H, CH═CH₂),1.51 (d,J=8.2 Hz, 8H, SiCH₂CH═CH₂), 1.32 (m, 8H, SiCH₂CH₂CH₂Si),0.62-0.53 (m, 16H, SiCH₂CH₂CH₂Si), 0.02 (s, 24H, Si(CH₃)₂). ¹³C NMR (100MHz, CDCl₃): δ135.21, 112.47, 23.49, 19.93, 18.55, 17.54, −3.52. HRMSCalcd for C₃₂H₆₇Si₅:591.4089 (M-H)+. Found: 591.4072. Anal. Calcd forC₃₂H₆₈Si₅:C, 64.78; H, 11.55. Found: C, 64.98; H, 11.55.

Example 13 Synthesis of Ar(CH₂)₂CO₂(CH₂)₃Si(Me)₂(CH₂)₃SiI₄ (29)

[0095] Si[(CH₂)₃Si(Me)₂CH═CH₂]₄ (28) (587 mg, 0.989 mmol) was weighedinto a 50 mL round-bottom flask and dissolved in 10 mL of THF. Thissolution was treated by cannula with freshly prepared 9-BBN (527 mg,4.69 mmol, 4.74 equiv) in 10 mL of THF. After 12 h of stirring at 22°C., 10 mL each of H₂O₂ (30% wt. solution in water), 2 M NaOH, andethanol were added. The mixture was then allowed to stir an additional12 h at 22° C. Water (100 mL) and Et₂O (100 mL) were added and theorganic layer was removed. The aqueous layer was washed with 2×100 mL ofEt₂O. The combined organic layers were dried over MgSO₄ and filtered.Removal of volatiles gave a crude oil that was purified by silica gelchromatography (TLC R_(f)=0.36 in EtOAc). ¹H NMR analysis (400 MHz)indicated that the product contained minor impurities (includingcyclooctadiol) which made characterization of the material difficult.Thus, the crude product was carried directly into the next step. Thetetraol was transferred to a 25 mL round-bottom flask, dissolved in 15mL of CH₂Cl₂, and cooled to 0° C.1-(p-isopropoxy-m-vinylphenyl)propionic acid (26) (1.02 g, 4.35 mmol,4.4 equiv), EDC (912 mg, 4.76 mmol, 4.8 equiv), and DMAP (61 mg, 0.50mmol, 0.50 equiv) were then directly added in succession to the mixtureas solids. The resulting mixture was stirred for 4 h and quenched with 2mL of a 10% citric acid solution. Additional water was added (200 mL)and the aqueous layer was washed with 3×100 mL of Et₂O. The combinedorganic layers were washed with 1 volume each of a saturated solution ofsodium chloride and water. Drying over MgSO₄, filtration, andconcentration gave a crude oil which was purified by silica gelchromatography (TLC R_(f) 0.36 in 4:1 hexanes:EtOAc). The desiredtetra(ester) was recovered as a colorless oil (954 mg, 0.623 mmol, 63%).IR (NaCl): 2974 (m), 2951 (m), 2919 (s), 2873 (m), 2855 (m), 1735 (s),1627 (w), 1491 (m), 1451 (w), 1384 (w), 1372 (w), 1293 (w), 1247 (s),1139 (m), 1119(m), 958 (w), 906 (w), 837 (m). ¹H NMR (400 MHz, CDCl₃):87.30 (d, J=2.4 Hz, 4H, aromatic CH), 7.02 (d, J=6.4 Hz, 4H, aromaticCH), 7.02 (dd, J=19.8, 9.4 Hz, 4H, ArCHCH₂), 6.79 (d, J=8.8 H 4H,aromatic CH), 5.71 (dd,J=17.8, 1.6 Hz, 4H, ArCHCH₂), 5.21 (dd, J=11.4,1.6 Hz, 4H, ArCHCH₂)) 4.48 (septet, J=6.2 Hz, 4H, (CH₃)₂CHOAr), 4.01 (t,J=7.0 Hz, 8H, CO₂CH₂), 2.88 (t, J7.8 Hz, 8H, ArCH₂CH₂CO₂), 2.59 (t,J=7.8 Hz, 8H, ArCH₂CH₂CO₂), 1.58 (m, 8H, CO₂CH₂CH₂CH₂Si(Me)₂), 1.36-1.25(m, 8H, SiCH₂CH₂CH₂Si(Me)₂), 1.33 (d, J=5.6 Hz, 24H, (CH₃)₂CHOAr),0.58-0.52 (m, 16H, CH₂Si(Me)₂CH₂), 0.47-0.42 (m, 8H, Si(CH₂)₄), −0.04(s, 24H, Si(Me)₂). ¹³C NMR (100 MHz, CDCl₃): δ172.77, 153.44, 132.40,131.76, 128.30, 127.61, 126.14, 114.30, 113.78, 70.96, 67.16, 36.30,30.38, 23.33, 22.33, 20.20, 18.65, 17.63, 11.30 −3.26. LRMS Calcd forC₈₈H₁₄₀O₁₂Si₅K (M+K): 1569.9. Found: 1569.5. Anal. Calcd forC₈₈H₁₄₀O₁₂Si₅: C, 69.06; H, 9.22. Found: C, 69.31; H, 9.36.

Example 14 Synthesis of[(PCy₃)Cl₂Ru═CH-o-O-i-PrC₆H₃(CH₂)₂COO(CH₂)₃Si(Me)₂CH₂₃Si]₄ (Formula 30)

[0096] (PCy₃)₂Cl₂Ru═CHPh (2) (792 mg, 0.962 mmol, 4.3 equiv) and CuCl(106 mg, 1.07 mmol, 4.8 equiv) were added to a 25 mL round-bottom flaskand suspended in 12 mL of CH₂C1₂. Dendrimer 29 (341 mg, 0.223 mmol, 1.0equiv) was added to this mixture through a cannula in 10 mL of CH₂C1₂.The mixture was stirred for a period of 3 h at 22° C., during which timethe original purple solution turned dark brown in color. The followingwork-up procedures were conducted in air with reagent-grade solvents.The mixture was concentrated at reduced pressure and passed through ashort plug of silica gel in 3:2 hexanes:Et₂O (brown band rapidlyelutes). Product fractions were pooled and concentrated. This materialwas passed through a second column of silica gel, this time with agradient elution (1:1 hexanes:CH₂Cl₂ to 2:3 hexanes:CH₂Cl₂ to 1:3hexanes:CH₂Cl₂ to 100% CH₂Cl₂). Finally, the column was flushed withEt₂O, at which point the product elutes (brown band). Solvent removalafforded a dark brown crystalline solid (637 mg, 0.194 mmol, 87%). IR(NaCl): 2927 (s), 2852 (s), 1955 (w), 1733 (s), 1684 (w), 1610 (w), 1582(w), 1488 (m), 1447 (m), 1417 (w), 1385 (m), 1296 (w), 1247 (m), 1222(m), 1204 (m), 1134 (m), 1104 (m), 913 (w), 891 (w), 849 (m), 774 (w),735 (m), 702 (w). ¹H NMR (400 MHz, CDCl₃): δ17.38 (d, J=4.0 Hz, 4H,Ru═CHAr), 7.52 (s, 4H, aromatic CH), 7.46 (d, J=8.8 Hz, 4H, aromaticCH), 6.98 d, J=8.8 Hz, 4H, aromatic CH), 5.23 (septet, J=6.2 Hz, 4H,(CH₃)₂CHOAr), 4.03 (t, J=7.1 Hz, 8H, CO₂CH₂), 3.03 (t, J=7.7 Hz, 8H,ArCH₂CH₂CO₂), 2.64 (t, J=7.7 Hz, 8H, ArCH₂CH₂CO₂) 2.32 (m, 12H, PCH),2.20-1.20 (m, 136H, CO₂CH₂CH₂CH₂Si(Me)₂, SiCH₂CH₂CH₂Si(Me)₂, andP(CH(CH₂)₅)₃), 1.79 (d, J=6.2 Hz, 24H, (CH₃)₂CHOAr), 0.60-0.52 (m, 16H,CH₂Si(Me)₂CH₂), 0.50-0.45 (m, 8H, Si(CH₂)₄), −0.03 (s, 24H, Si(Me)₂).¹³C NMR (100 MHz, CDCl₃): δ279.24 172.60, 151.29, 143.79, 134.69,129.42, 122.51 (d, J_(OC)=5.9 Hz), 113.19, 75.50 (d, J_(OC)=7.8 Hz),67.27, 36.36, 35.67 (d, J_(PH)=24.4 Hz), 30.14, 29.73, 27.80 (d,J_(PH)=10.7 Hz), 26.33, 23.26, 22.14, 20.14,18.58, 17.56, 11.26, −3.33.^(3l)P NMR (162 MHz, CDCl₃): δ59.17 (s, PCy₃). LRMS Calcd forC₁₅₆H₂₆₄C₁₈O₁₂P₄Ru₄Si₅Na₂ (M+2Na)+: 3331.2. Found: 3331.8. Anal. Calcdfor C₁₅₆H₂₆₄Cl₈O₁₂P₄Ru₄Si₅: C, 57.05; H, 8.10. Found: C, 56.80; H, 8.00.

Example 15 Synthesis of [(4,5-dihydrolMES) Cl₂Ru═CH-o-O-i-PrC₆H₃(CH₂)₂COO(CH₂)₃Si(Me)₂(CH₂)₃Si]₄ (formula 31).

[0097] The unmetallated dendrimer (227 mg, 0.148 mmol, 1.0 equiv) wasweighed into a 25 mL round-bottom flask and dissolved in 15 mL ofCH₂Cl₂. (4,5-dihydrolMES)(PCy₃)Cl₂Ru═CHPh (3) (606 mg, 0.714 mmol, andCuCl (72.0 mg, 0.731 mmol, 4.9 equiv) were added directly to thissolution as solids. The mixture was stirred for 2 h at 22° C., duringwhich time the original purple solution turned a dark green/brown color.The following work-up procedures were conducted in air using reagentgrade solvents. The mixture was concentrated at reduced pressure andpassed through a short column of silica gel using a gradient elution(100% CH₂Cl₂ to 4:1 hexanes:Et₂O to 1:1 hexanes: Et₂O to 100% Et₂O). Thegreen band was collected and concentrated, affording a greenmicrocrystallinie solid (277 mg, 0.08 16 mmol, 55%). IR (NaCl): 3432(b), 2915 (m), 1732 (s), 1632 (w), 1607 (w), 1595 (w), 1487 (s), 1418(m), 1259 (s), 1221 (m), 1132 (m), 1104 (m), (w), 912 (w), 849 (w), 579(w). ¹H NMR (300 MHz, CDCl₃): δ16.51 (s, 4H, Ru═CHAr), 7.33 (d, J=7.0Hz, 4H, aromatic CH), 7.07 (s, 16H, mesityl aromatic CH), 6.74-6.66 (m,8H, aromatic CH), 4.85 (septet, J=6.3 Hz, 4H, (CH₃)₂CHOAr), 4.17 (s,16H, N(CH₂)₂N), 4.02 (t, J=7.0 Hz, 8H, CO₂CH₂), 2.91 (t, J=7.8 Hz, 8H,ArCH₂CH₂CO₂), 2.53 (t, J=7.8 Hz,8H, ArCH₂CH₂CO₂), 2.47 (s, 48H, mesitylo-CH₃), 2.41 (s, 24H, mesityl pCH₃), 1.61 (m, 8H, CO₂CH₂CH₂CH₂Si(Me)₂),1.40-1.25 (m, 8H, SiCH₂CH₂CH₂Si(Me)₂), 1.23 (d, J=6.3 Hz, 24H,(CH₃)₂CHOAr), 0.61-0.45 (m, 24H, CH₂Si(Me)₂CH₂ and Si(CH₂)₄), −0.02 (s,24H, Si(Me)₂). ¹³C NMR (75 MHz, CDCl₃): δ297.07 (d, J=166.0 Hz), 211.32,172.81, 150.80, 145.16, 138.76, 134.28, 130.42, 130.29, 129.80, 129.39,128.74, 128.22, 74.41, 67.19, 51.44, 36.03, 29.54, 23.14, 21.53, 20.96,20.60, 20.03, 18.48, 17.47, 11.12,-4.13. LRMS Calcd forC₁₆₈H₂₄₀Cl₈N₈O₁₂Ru⁴Si₅(M+4H):3393.1. Found: 3393.1. Anal. Calcd forC₁₆₈H₂₃₆Cl₈N₈O₁₂Ru₄Si₅: C, 59.56; H, 7.02. Found: C, 59.55; H, 6.96.

Example 16 Representative Experimental Procedure For RCM Catalyzed byMonomer (4,5 dihydrolMES)Cl₂Ru═CH-o-O-i-PrC₆H₄ (formula 5)

[0098] Triene (7) (50.1 mg, 0.329 mmol, 1.0 equiv) was weighed out in a25 mL round-bottom flask and dissolved in 3 mL of CH₂Cl₂ (0.1 M).(4,5-dihydrolMES)Cl₂RuCH-o-O-i-PrC₆H₄ (5) (9.80 mg, 0.0 156 mmol 0.0474equiv) was added as a solid and the resulting deep green solution wasstirred at 22° C. TLC analysis after 10 mm indicated completion of thereaction. As usual, work-up procedures were conducted in air usingreagent-grade solvents. The mixture was concentrated at reduced pressureand passed through a short column of silica gel in 2:1 hexanes:CH₂Cl₂affording diene (8) (33.4 mg 0.269 mmol, 82%) as a colorless oil (TLCR_(f)=0.46 in 9:1 hexanes:Et₂O). The catalyst was then retrieved as agreen solid by flushing the silica column with 100% CH₂Cl₂ (9.60 mg, 0.0153 mmol, 98%).

Example 17 Representative Experimental Procedure for RCM Catalyzed byDendritic [(PCY₃)Cl₂Ru═CH-o-O-i-PrC₆H₃(CH₂)₂COO(CH₂)₃Si(Me)₂(CH₂)₃Si]₄(formula 30)

[0099] Tosyl amide (32) (250 mg, 0.995 mmol, 1.0 equiv) and dendriticcatalyst (30) (43.9 mg, 0.0140 mmol, 0.014 equiv) were weighed into a 50mL round-bottom flask. The flask was equipped with a reflux condenser,evacuated, and filled with an atmosphere of argon. The vessel wascharged with CH₂Cl₂ (20 mL, 0.05 M) and submerged into an oil bathpreheated to 45° C. The reaction was stirred for 15 minutes, at whichpoint TLC analysis indicated completion of the reaction. Removal of thesolvent in vacuo afforded a dark brown oil that was purified by silicagel chromatography (100% CH₂Cl₂), affording 33 as a white solid (219 mg,0.983 mmol, 99%). The column was then flushed with 100% Et₂O to recoverthe dendritic catalyst as a brown solid residue (46.2 mg, 0.0141 mmol,100%). The recovered catalyst was transferred directly into a new flaskfor a subsequent reaction. As discussed above, Ru recovery on thedendrimer could be quickly analyzed upon inspection of the ¹H NMR (400MHz) spectrum. Integration of the benzylic methylene protons at 3.03 ppm(metal-occupied sites) and 2.88 ppm (metal-vacant sites) provided aratio of 88:12 respectively.

Example 18 Experimental Procedure for RCM Catalyzed by Dendritic[(4,5-dihydrolMES) C12Ru═CH-o-O-i-PrC₆H₃(CH₂)₂COO(CH₂)₃5i(Me)₂(CH₂)₃Si]4formula 31)

[0100] Diene (11) (32.7 mg, 0.233 mmol, 1.0 equiv) was weighed into a 25mL round-bottom flask and dissolved in 5 mL of CH₂Cl₂ (0.05 M).Dendritic catalyst 31 (12.4 mg, 0.00366 mmol, 0.016 equiv) was added asa solid and the solution was allowed to stir at 22° C. TLC analysisafter 2 h indicated completion of the reaction. Work-up proceduresproceeded in air with reagent-grade solvents. The mixture wasconcentrated at reduced pressure and passed through a short plug ofsilica gel in 100% CH₂Cl₂, affording (12) (20.4 mg, 0.1819 mmol, 78%) asa colorless oil (TLC R_(f)=0.25 in 4:1 hexanes:Et₂O). The catalyst wasthen flushed off of the column with 100% Et₂O affording 12.3 mg (0.00363mmol, 99%) of a green solid. Ru recovery on the dendrimer was assessedusing ¹H NMR spectroscopy (400 MHz). Integration of the isopropoxymethine proton for both metal-occupied (4.90 ppm) and metal-vacant (5.71ppm) sites gave a ratio of 92:8 respectively, indicative of 8% metalloss.

Example 19 Synthesis of an Immobilized Catalyst

[0101] This procedure allows installment of the linker and the activemetal complex in a single step. Treatment of the compound 3 with astoichiometric amount of(4,5-dihydrolMES)(PCy₃) Cl₂Ru═CHPh in thepresence of allylchlorodimethylsilane led to successful ring-openingcross metathesis and metallation of the styrenyl ether “docking site.”Subsequent diffusion of this product into the pores of a sol gel sample(200 A° pore size glass monoliths, available from Geltech, Orlando,Fla.) resulted in a substitution reaction involving the labile Si-C1bondwith the free hydroxyl groups on the glass surface. After extensivewashing and drying in vacuo, a bright green glass pellet (Formula 6) wasrecovered which showed good activity in the RCM of the terminal diene 44(0.10 mmol scale) to yield 45 (as shown in Scheme 7). The immobilizedcatalyst was then carried through three iterative rounds of metathesisto covert diene 44 to the cyclic compound 45 as shown below.

[0102] Although successive ring-closures required longer reactiontimes, >90% conversion was observed in each case, the following factorswere observed: (1) Derivatization of the sol gel pellet resulted in a1.0 mg increase in mass. Calculations therefore suggest that the RCM ofcompound 7 was mediated by a very small amount of active catalyst (˜1mol %). This may partly account for the slow reaction rate, particularlyin the second and third cycles. Increasing the catalyst loading to 5 mol% will lead to dramatic improvements in reaction rate. (2) In contrastto reactions run with 5 mol % Formula 1 or 5, the spectrum of theunpurified reaction mixture consisted of >98% pure cycloolefin (nocatalyst or byproduct thereof could be detected). (3) No filtration stepwas required to isolate the product. The reaction mixture was simplyremoved with a Pasteur pipette, the glass sample was washed with CH₂Cl₂,and fresh substrate was added.

[0103] Although the invention has been described in detail for thepurpose of illustration, it is understood that such detail is solely forthis purpose, and variations can be made therein by those skilled in theart without departing from the spirit and scope of the invention asdescribed by the appended claims.

What is claimed is:
 1. A composition comprising a transition metalcatalyst having the following structure:

wherein: comprises a transition metal; R comprises an alkyl, alkenyl,alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxy carbonyl,alkylamino, alkylthio, alkylsulfonyl, alkylsulfinyl; each optionallysubstituted with an alkyl, halogen, alkoxy, aryl or heteroaryl moiety;R₁ and R₂ each comprises, or together comprise, an electron withdrawinganionic ligand; a, b, c, and d each comprises H, a halogen atom or analkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy,alkoxycarbonyl, alkylamino, alkylthio, alkylsulfonyl; alkylsulfinyl;each optionally substituted with an alkyl, halogen, aryl or heteroarylmoiety; and Y comprises an electron-donating heterocyclic carbeneligand.
 2. The composition of claim 1 wherein M is Ru.
 3. Thecomposition of claim 1 wherein X is O.
 4. The composition of claim 1wherein R is a lower alkyl group.
 5. The composition of claim 4 whereinR is isopropyl.
 6. The composition of claim 1 wherein R₁ and R₂ each isa halogen.
 7. The composition of claim 6 wherein R₁ and R₂ each is Cl.8. The composition of claim 1 wherein a, b, c, and d each comprises H ora lower alkyl group.
 9. The composition of claim 1 wherein Y comprises a4,5-dihydroimidazol-2-ylidene.
 10. The composition of claim 9 wherein Ycomprises a tricyclic aromatic ring structure having the followingstructure:

wherein R₃ and R₄ each comprises an aromatic ring moiety.
 11. Thecomposition of claim 10 wherein R₃ and R₄ comprise both comprise2,4,6-trimethylphenyl (mesityl) moieties.
 12. The composition of claim 1comprising the following structure:


13. A composition of claim 1 wherein the transition metal catalyst ispart of a dendrimer compound.
 14. The transition metal catalyst of claim13 having the following structure:

wherein A is a polyvalent atom selected from the group consisting ofcarbon, nitrogen, silicon and phosphorous; R₅, R₆, R₇ and R₈ eachcomprises the following structure:

 wherein: M comprises a transition metal; X comprises O, S, N or P; Rcomprises an alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy,alkynyloxy, aryloxy, alkoxy carbonyl, alkylamino, alkylthio,alkylsulfonyl, alkylsulfinyl; each optionally submitted with an alkyl,halogen, aryl or heteroaryl moiety; R₁ and R₂ each comprises, ortogether comprise, an electron withdrawing group; and Z comprises Y or aphosphine group.
 15. The composition of claim 14 wherein A is silicon.16. The composition of claim 14 wherein M is a transition metal.
 17. Thecomposition of claim 14 wherein M is ruthenium
 18. The composition ofclaim 14 wherein X is O.
 19. The composition of claim 14 wherein R is alower alkyl group.
 20. The composition of claim 19 wherein R isisopropyl.
 21. The composition of claim 14 wherein R₁ and R₂ each is ahalogen.
 22. The composition of claim 21 wherein R₁ and R₂ each is C1.23. The composition of claim 14 wherein Z comprises a phosphine moietyhaving the formula P(Cy)₃.
 24. The composition of claim 23 wherein Cycomprises an aliphatic ring structure.
 25. The composition of claim 23wherein Cy comprises a cyclohexyl or cyclopentyl group.
 26. Thecomposition of claim 14 wherein Z comprises an aromatic ring structurehaving the following structure:

wherein: R₃ and R₄ each comprises an aromatic ring moiety.
 27. Thecomposition of claim 26 wherein R₃ and R₄ each comprises 2, 4,6-trimethylphenyl(mesityl).
 28. The composition of claim 14 comprisingthe following structures:


29. The composition of claim 1 wherein the transition metal catalyst ispart of a polymeric compound.
 30. The composition of claim 1 wherein thetransition metal catalyst is chemically bound to a substrate surface.31. The transition metal catalyst of claim 30 comprising at least onesubstituent that is capable of reacting with functional groups on thesubstrate surface so as to render the said catalyst chemically bonded tothe said substrate surface.
 32. The transition metal catalyst of claim31 wherein the substituent is selected from the group consisting ofalkyl halosilanes, alkenyl halosilanes, alkoxy halosilanes, aryloxyhalosilanes, aryl halosilanes, akyl halides, cycloalkyl halides, alkenylhalides, cycloalkenyl halides, aromatic and heteroaromatic halides, acidchlorides, anhydrides, succimidyl esters, epoxides, thiols, acrylate,methacrylate, acrylamide, methacrylamide, benzophenone, and derivativesthereof.
 33. The transition metal catalyst of claim 32 wherein thesubstituent is alkylldimethylsilylcholride.
 34. A composition of claim 1wherein the said catalyst is capable of chemically bonding to asubstrate surface.
 35. A composition of claim 30 wherein the substrateis a porous or a non-porous solid phase.
 36. A composition of claim 30wherein the substrate is glass, metal, non-metal, ceramics, rubber or apolymeric material.
 37. A composition of claim 30 wherein the substrateis part of a containing vessel.
 38. A composition of claim 37 whereinthe containing vessel is a chemical reactor.
 39. A method ofimmobilizing the transition metal catalyst of claim 1 comprising thesteps of i) reacting the said catalyst with a chemical coupling agentunder conditions to form an adduct with said catalyst so as to render itcapable of attachment to a substrate surface, and ii) contacting saidadduct with a substrate or a substrate surface under conditions to causesaid adduct to become chemically bound to said substrate surface throughcovalent chemical bonding, ionic bonding, non-ionic interaction, orcombinations thereof.
 40. A method of claim 39 wherein the catalyst is atransition metal catalyst capable of reacting with a chemical couplingagent that is chemically bonded to a substrate surface.
 41. A method ofclaim 40 wherein the chemical coupling agent comprises a compoundcontaining at least one alkyl halosilanes, alkenyl halosilanes, alkoxyhalosilanes, aryloxy halosilanes and aryl halosilanes, akyl andcycloalkyl halides, alkenyl and cycloalkenyl halides, aromatic andheteroaromatic halides, acid chlorides, anhydrides, succimidyl esters,epoxides and thiols.
 42. The method of claim 41 wherein the chemicalcoupling agent is allylchloro-dimethylsilane.
 43. The method of claim 39wherein the said transition metal catalyst is reacted with a pluralityof chemically different coupling agents.
 44. The method of claim 39wherein the substrate is glass, metal, non-metal, ceramics, rubber or apolymeric material.
 45. The method of claim 39 wherein the saidsubstrate material is a porous or non-porous material.
 46. The method ofclaim 45 wherein the said substrate material is a porous sol-gel. 47.The method of claim 45 wherein the said substrate material is a solidphase inorganic gel.
 48. The method of claim 47 wherein the saidsubstrate material is a glass mono-lithic gel.